Gallium arsenide semiconductor devices fabricated with insulator layer

ABSTRACT

An insulator layer for single crystal gallium arsenide substrates in which the insulator layer is compliantly matched with the substrate and the insulator layer is free of defects causing surface roughness and crystalline defect problems which, otherwise, could impair device performance. To accomplish this, the insulator layer is formed on a gallium arsenide substrate as an integral composite or variegated structure including (a) a uniform homogenous film of Group IIa metal atoms attached directly onto a gallium arsenide substrate surface in the form of a monolayer, and (b) a single crystal epitaxial film of a Group IIa metal fluoride deposited on the monolayer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of copending application Ser. No. 09/197,440 filedon Nov. 23, 1998.

This is a continuation-in-part of U.S. patent application Ser. No.08/624,847, filed Mar. 25, 1996, now U.S. patent application No.5,932,006, which is a divisional of U.S. patent application Ser. No.08/246,206, filed May 19, 1994, which is abandoned.

BACKGROUND OF THE INVENTION

This invention relates generally to insulator layers for galliumarsenide semiconductor devices and, more particularly, to insulatorlayers derived from Group IIa metal fluorides which are formed on singlecrystal gallium arsenide substrates.

Materials used in semiconductor devices must have good semiconductingproperties, good electron mobility, and the ability to host aninsulating material. Several materials are available which have goodsemiconducting properties and good electron mobilities but which areunsuitable because a good insulator cannot be formed on them. Silicon,however, is widely used in semiconductor devices because silicon dioxideforms naturally on silicon and silicon dioxide is a good insulator. Thedisadvantage of silicon is that its mobility is not as high as othersemiconductors and silicon dioxide is not the strongest insulatoravailable. This means that compromises in speed and performance are madewhen silicon is used in electronic devices.

Gallium arsenide (GaAs) is also a semiconductor and is used in someelectronic applications. A device made out of GaAs would be faster thanthe same device made out of silicon because GaAs has an electronmobility that is considerably higher than that of silicon.Unfortunately, there is no native insulating oxide suitable for GaAselectronic devices. Also, many opto-electronic devices using GaAssubstrates rely on epitaxial insulator/semiconductor heterostructureswith abrupt interfaces which further increases the challenge of findinga suitable insulator for GaAs substrates for these applications.

Several materials have been used to provide insulating films on III-Vcompound semiconductor devices. Some of these films were previously usedon silicon semiconductor devices. Examples of these film materialsinclude SiO₂, Si₃N₄, Al₂O₃, and P₂O₃ films. New films have also beendeveloped specifically for the III-V compound semiconductors. Forinstance, A. J. Shuskus (U.S. Pat. No. 4,546,372) developed anessentially oxygen-free, amorphous, phosphorous-nitrogen glasspassivating film for III-V compound semiconductors. Similarly, J.Nishizawa et al. (U.S. Pat. No. 4,436,770) disclose new galliumoxynitride and aluminum oxynitride insulating films for III-V compoundsemiconductors. However, these materials have found only limitedapplication.

Although the high dielectric strength of barium fluoride (BaF₂) (100)makes it a potentially interesting candidate as an insulating material,unfortunately BaF₂ and GaAs are severely lattice mismatched (˜10%mismatched), which is a condition previously considered to bedetrimental to epitaxial growth. The lattice mismatch problem has notbeen the only condition hindering the growth of epitaxial BaF₂ (100) onGaAs. It is known that the (100) face of the cubic fluorite structure ofbarium fluoride has a surface free energy far in excess of the (111)face. See, L. J. Schowalter et al., CRC Critical reviews in Solid Stateand Materials Sciences, pp. 367 (1989). For this reason, it has beenthought that (111) growth is favored over (100) growth. Even when (100)growth is achieved, surface free energy considerations predict facetingof the (100) growth front into (111) asperites. This behavior has beenobserved for CaF₂, as described in the above-cited Schowalter et al.publication, and BaF₂, as described by M. F. Stumborg et al., J. Appl.Phys. 77(6), 2739 (1995).

Clemens el al., J. Appl. Phys. 66(4), 1680 (1989), reported being ableto grow (100)-oriented BaF₂ on GaAs, but the orientation switched to(111) after only ˜20 Å of film thickness. Furthermore, streaky RHEEDpatterns were not observed until the (111) orientations began todominate. Films grown with a 400° C. substrate temperature exhibitedsigns of misoriented mosaic structures (i.e., rings in the RHEEDpatterns). Depositions at higher temperatures (580° C.) did not yieldstreaky RHEED patterns, leading Clemens el al. to state a conclusionthat no two-dimensional growth of (100)-oriented barium fluoride seemedpossible.

Truscott et al., J of Crystal Growth, 81, 552 (1987), also investigatedthe growth of BaF₂ on GaAs as well as the reverse heterostructure. Theyalso found temperature dependent RHEED patterns indicative of (100) and(111) growth modes. However, they reported no achievement oftwo-dimensional BaF₂ (100) layers. In fact, they reported their BaF₂films to be conducting, presumably due to Ga diffusion into the BaF₂layer.

In view of the above, it would be desirable to provide an improved thinfilm insulator for gallium arsenide electronic devices which yields highquality device characteristics such as high-break down voltage.

SUMMARY OF THE INVENTION

In accordance with this invention, a unique insulator layer for singlecrystal gallium arsenide substrates is provided in which the insulatorlayer is compliantly matched with the substrate and the insulator layeris free of defects causing surface roughness problems which could impairdevice performance.

To accomplish this, the insulator layer is formed on a gallium arsenidesubstrate as an integral composite or variegated structure including (1)a uniform homogenous film of Group IIa metal atoms attached directlyonto a gallium arsenide substrate surface in the form of a monolayer,and (2) a single crystal epitaxial film of a Group IIa metal fluoridedeposited on the monolayer.

To fabricate the uniform, defect-free homogenous film portion of theinsulator layer, the homogenous film is formed as the reaction productof a reaction between a Group IIa metal fluoride vapor and a galliumarsenide substrate surface in the presence of an arsenic gasoverpressure. The arsenic gas overpressure effectively causes amonolayer of group IIa metal atoms to attach and form directly upon thegallium arsenide substrate surface without unreacted metal atoms (i.e.,metal atoms not directly attached to the substrate surface) remaining inthe homogenous film when the reaction is completed (i.e., the monolayerformation is completed) and a deposition of the epitaxial film of GroupIIa metal fluoride onto the monolayer has commenced. The monolayerserves as a compliant interfacial layer that preventslattice-mismatching problems from arising as between the galliumarsenide substrate and the epitaxial metal fluoride layer. Since theinsulator layer can be fabricated in this manner in extremely thinsubmicron thicknesses while still being defect-free (i.e., withoutsurface roughness problems and other crystalline defects such asdislocations and stacking faults), gallium arsenide electroniccomponents which incorporate the insulator layer are endowed withsuperior break-down voltage characteristics, among other things.

The single crystal gallium arsenide substrate, upon which the insulatorlayer can be formed and utilized, may be a wafer or epitaxial layer ofgallium arsenide, or a gallium arsenide based semiconductor alloy or aheterostructure of super-lattice made of a combination of galliumarsenic based alloys, or any of these forms of gallium arsenide asprovided on another suitable substrate. Preferably, the single crystalgallium arsenide substrate surface and the single crystal epitaxialGroup IIa metal fluoride film both are (100) oriented. In anotherpreferred embodiment, the Group IIa metal fluoride used in fabricatingthe insulator film is barium fluoride.

A wide variety of gallium arsenide semiconductor devices can benefitfrom incorporating the insulator film of the present invention,including gallium arsenide metal insulator semiconductor field effecttransistors (MISFETs), charge couple devices (CCDs), integrated circuitcapacitors, nonvolatile memory, optical waveguides, and so forth.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features, aspects, and advantages of the presentinvention will become better understood with regard to the followingdescription, appended claims, and accompanying drawings where:

FIG. 1 is a schematic drawing of an insulator/gallium arsenide epitaxialstructure of the invention;

FIG. 2A is a schematic drawing of a depletion mode metal insulatorsemiconductor field effect transistor (MISFET) containing the epitaxialstructure of FIG. 1;

FIG. 2B is a schematic drawing of an enhancement mode MISFET containingthe epitaxial structure of FIG. 1;

FIG. 3 is a schematic of a charge coupled device (CCD) containing theepitaxial structure of FIG. 1;

FIGS. 4A and 4B are schematics of capacitor devices containing theepitaxial structure of FIG. 1;

FIG. 5 is a schematic drawing of a top view of a suitable test set upfor measuring the capacitance and the breakdown voltage of an insulatorlayer of this invention; and

FIG. 6 is a schematic of a nonvolatile memory device containing theepitaxial structure of FIG. 1.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The invention is directed to formation of improved insulators in galliumarsenide electronic devices such as metal insulator semiconductor fieldeffect transistors (MISFETs), charge coupled devices (CCDs), and circuitcapacitors.

Recent advances described in the present inventors' U.S. patentapplication Ser. No. 08/624,847, filed Mar. 25, 1996, now allowed, theteachings of which are incorporated herein by reference for allpurposes, address the lattice mismatch problem between GaAs and singlecrystal epitaxial barium fluoride by the creation of a compliant“template” layer on the GaAs (100) surface before BaF₂ deposition.Specifically, the surface is exposed to an extremely low flux of BaF₂molecules, leaving a monolayer of Ba on the surface while driving offexcess Ga and F as volatile GaF. Subsequently arriving BaF₂moleculesadhere to the surface as complete molecular units. The BaF₂ filmsdeposited on the compliant Ba monolayer are epitaxial. This presentinvention is an advancement of this technology in that newly developedprocessing techniques make it is possible to form a BaF₂ surface that isexceptionally smooth and uniform as it is devoid of any significantatomic level roughness that might otherwise impair the performance ofthe device.

The insulator layer of this invention is formed by exposing a clean, hotsingle crystal gallium arsenide substrate to barium fluoride vapor in anultrahigh vacuum environment with low background pressure with thepresence arsenic gas during early stages of the process of forming theinsulator. The barium fluoride is introduced in the ultrahigh vacuumenvironment maintained at a rate and temperature that permits the bariumfluoride to react with the gallium arsenide while it is subjected toarsenic gas treatment, to initially form a homogenous reaction productlayer, which is a monolayer of barium atoms less than 5 Å thick directlyattached to the substrate surface. Once the monolayer formation iscompleted, i.e., a continuous single layer of barium atoms has formedover the exposed surface regions of the GaAs substrate without leavingbare spots in such exposed regions, the arsenic gas introduction isdiscontinued while the introduction of the barium fluoride is continued.The reaction product layer, i.e., the monolayer, provides a surface uponwhich a single crystal epitaxial layer of barium fluoride will thendeposit in the same crystal orientation as the underlying single crystalgallium arsenide substrate. Since the monolayer forms relatively rapidly(e.g., generally within about 30 seconds or less), the arsenic gasoverpressure preferably should be created at the GaAs substrate surfacebefore the barium fluoride vapor flux is introduced.

Therefore, the temperature of the single crystal, gallium arsenidesubstrate and the barium fluoride vapor flux rate are adjusted, as wellas the arsenic gas pressure, to allow the complete formation of theuniform monolayer before single crystal epitaxial barium fluoride can bedeposited. The thickness of the monolayer is self-limiting. After amonolayer is formed, the arsenic gas is eliminated and the bariumfluoride vapor flux continued at the same or a greater rate to deposit asingle crystal epitaxial layer of barium fluoride on the monolayer(i.e., the reaction product layer). If the barium fluoride is depositedtoo rapidly before a uniform monolayer is completely formed, epitaxialgrowth of barium fluoride will occur in those places where the reactionproduct is first completed and a three dimensional island mode of bariumfluoride growth will result, which is undesirable. Channels between thebarium fluoride islands present paths of conduction that degrade theinsulative properties of the barium fluoride. This problem is avoidedwhen, according to this invention, care is taken to slowly depositbarium fluoride initially so that a uniform monolayer is properly formedin the presence of the arsenic gas before substantial barium fluorideepitaxial formation begins. When this care is taken, the barium fluoridewill deposit as a uniform, two-dimensional single crystal, epitaxiallayer which is an excellent insulator.

While not desiring to be bound to any particular theory at this time, itnonetheless is thought that the distinctions between the successfuldeposition of two-dimensional BaF₂ (100) in the present invention andprevious efforts by others are at least two-fold: firstly, the presenceof the arsenic overpressure before and during the initial stages of BaF₂deposition replaces the volatile arsenic layer expelled from the GaAs(100) surface under these deposition conditions. Secondly, the low BaF₂flux rate used permits the chemical interaction to run its course beforethe BaF₂ epitaxy begins. This low BaF₂ flux is only required long enoughto form the compliant Ba monolayer. Once the compliant layer is formed,the BaF₂ flux can be increased without detrimental effects to theepitaxial quality of the BaF₂.

If no overpressure of arsenic gas back pressure is provided before andinitially during deposition of the single crystal epitaxial layer ofbarium fluoride on the underlying homogenous layer, it is observed thata rough surface forms on the GaAs substrate which is replicated in theoverlying insulator layer. This rough surface undermines the ability toachieve device quality insulation and high break down voltages. Therough surface, which is avoided and eliminated by the present invention,is thought to be attributable to barium atoms left present at thereaction product layer formed between the BaF₂ and the GaAs. The atomicbarium is thought to occur at the barium fluoride/gallium arsenidereaction interface because gallium atoms in the GaAs substrate tend toform dimers with each other in the absence of the arsenic gasoverpressure, which, in turn, react with fluoride species from thebarium fluoride reactant to form gallium fluoride gas molecules that areexhausted from the reaction chamber, leaving barium atoms behind at thereaction interface which are not directly attached to the substratesurface, creating defects that roughen the surface of the completedinsulator layer formed on the GaAs substrate. Therefore, the arsenic gasis introduced at a rate that is just enough to scavenge for any excessbarium atoms that would otherwise remain behind to create defects on theGaAs surface.

The arsenic gas, i.e., As, As₂ and/or As₄, that is used to create theback pressure in the MBE chamber during initial barium fluoride vaporflux can be derived directly from a Knudsen or effusion cell of a MBEapparatus for supplying this element, or, alternatively, the arsenic gascan be derived from a precursor pumped into the MBE chamber, e.g. arsine(AsH₃), which is unstable and decomposes into tetraatomic arsenicmolecules and hydrogen when heated.

The arsenic vapor/barium fluoride vapor rates ratio and time duration ofthe arsenic vapor treatment of the GaAs substrate are importantparameters for the formation of the BaF₂ insulator layer of thisinvention. For BaF₂ growth, the arsenic/BaF₂ flux ratio generally canrange from 20/1 to 1/4 (millibar arsenic/millibar BaF₂ units), and theduration of time for which this flux ratio is maintained ranges frombetween about 15 seconds to 60 seconds. Preferably, for BaF₂ depositionupon a GaAs substrate, the arsenic/BaF₂ flux ratio preferably should beapproximately 10/1 (millibar arsenic/millibar BaF₂ units) and theduration of time for which this flux ratio is maintained ranges frombetween about 15 seconds to 60 seconds. This preferred 10/1 flux ratioapplies as long as the arsenic flux is in the 10⁻⁶ millibar range andthe BaF₂ flux is in the 10⁻⁷ millibar range. For example, suitable fluxratios meeting this condition would include, for example, 1.0×10⁻⁶millibar arsenic/1.0×10⁻⁷ millibar BaF₂, 3.0×10⁻⁶ millibararsenic/3.0×10⁻⁷ millibar BaF₂, 5.0×10⁻⁶ millibar arsenic/5.0×10⁻⁷millibar BaF₂, and so forth. In one preferred embodiment, an arsenicflux of 1.0×10⁻⁶ millibar arsenic and a BaF₂ flux of 1.0×10⁻⁷ millibaris created in the MBE chamber in the presence of the GaAs substrate fora concurrent period of time of 15 seconds. While the detaileddescriptions herein exemplify the use of barium fluoride as the compoundused to form the insulator layer for sake of illustration, it will beappreciated that other Group IIa metal fluorides, such as calciumfluoride and strontium fluoride, also can be used in a similar manner inthe practice of this invention instead of barium fluoride. The Group IIametal atoms of barium, strontium, and calcium have a size (i.e., thediameter of the largest electron orbital) of less than 5 Å, i.e., theatomic diameter of barium is 4.48 Å, and that of strontium is 4.29 Å,and that of calcium is 3.94 Å. It therefore can be appreciated how theformation of a monolayer of these metal atoms, for example, on a GaAssubstrate by the techniques presented herein, permits the formation ofan extremely thin, yet effective compliant layer upon which a singlecrystal epitaxial metal fluoride can be provided. The thickness of auniform monolayer of Ba, Sr, or Ca atoms, as formed by the presentinvention, will be greater than zero and less than 5 Å.

In one preferred mode of this invention, a single crystal GaAs epitaxiallayer (“epilayer”) substrate is formed on a standard commercial gradesingle crystal gallium arsenide crystal wafer or other suitablesubstrate for a GaAs epilayer, in a commercial molecular beam epitaxial(MBE) deposition chamber, such as model Semicon V8OH made by VacuumGenerators, having a standard substrate heater. Both gallium and arsenicfluxes are concurrently provided to grow the epitaxial GaAs. The GaAswafer preferably is chemically wet-etched before being introduced to thegrowth chamber to improve its surface morphology. Single crystal GaAsepilayer deposition is stopped when a streaky RHEED pattern is observed.The deposition of GaAs is stopped by closing the Ga source; however, thearsenic source is left open to maintain the improved morphology. The MBEchamber is evacuated to a background pressure of preferably less than10⁻⁹ millibars, more preferably less than 10⁻¹⁰ millibars, and stillmore preferably less than 10⁻¹¹ millibars and is trapped with liquidnitrogen. Then a BaF₂ shutter is opened. After a brief period of time(e.g., about 15 to 60 seconds) sufficient to permit a uniformtwo-dimensional monolayer of barium atoms to form on the surface of theGaAs epilayer, the arsenic gas shutter is closed while the BaF₂ shutterremains open to vapor deposit barium fluoride on the monolayer. As willbe appreciated from a practical standpoint, the mechanics necessary foropening/closing the various source gas shutters to the MBE chamber,according to the protocol described above, cannot be executedinstantaneously and that certain very brief time periods will beassociated with completely opening or closing the respective effusioncell shutters, as necessary, such that flux concentrations will brieflytransition in the chamber. However, these inadvertent brief transitionperiods for the fluxes have not been found to adversely effect theresults. The barium fluoride flux rate preferably is such as to providea monolayer formation within about 60 seconds or less, and morepreferably, in less than 30 seconds, at an approximately 700° C.substrate temperature. The rate of the barium fluoride vapor must beslow enough to permit the complete formation of the monolayer reactionproduct layer before barium fluoride molecules begin to deposit (growepitaxially) on the monolayer reaction product. The temperature rangegiven above is the substrate heater temperature. The actual substrate isat a somewhat lower temperature. This is true for other commercialsubstrate heaters and is understood, by those of ordinary skill in thisart. Moreover, heater temperatures over the range of from 500° C. to700° C. produce the same uniform, monolayer. Substrate heatertemperature ranges are preferably from 500° C. to 700° C., morepreferably from 550° C. to 700° C. and still more preferably from 575°C. to 700° C. At heater temperatures near the lower end of the range,the deposition rate is decreased to permit the complete formation of thereaction layer before a substantial amount of barium fluoride isdeposited.

The same monolayer reaction product is consistently produced even atdifferent substrate heater temperatures over the range of 500° C. to700° C. Moreover, the reaction product can be characterized by a numberof physical properties. First, the RHEED pattern of the monolayerreaction product is similar to that of BaF₂ (same symmetry, differentspot shapes). Next, XPS results indicate lower Ba 3d bonding energiesthan those of BaF₂. Most important, uniform single crystal, epitaxialbarium fluoride is deposited on single crystal gallium arsenidesubstrates that are coated with a uniform monolayer under conditionsthat would have produced amorphous or polycrystalline barium fluoride ona bare, clean single crystal gallium arsenide substrate without themonolayer reaction product layer. It is the deposition of the uniformsingle crystal, epitaxial barium fluoride layer that confirms that thedesired uniform two-dimensional monolayer is present.

The same results, in terms of forming the uniform monolayer on a GaAssubstrate, can be achieved using a preformed substrate having a GaAsepilayer film already grown on a substrate from a separate previousprocessing operation or as obtained as such from a supplier, by heatingthe preformed GaAs epilayer film and substrate in arsenic vapor untilthe film reaches the appropriate temperature for BaF₂ deposition. Then,the BaF₂ deposition is performed.

Once the uniform monolayer has been formed on a single crystal galliumarsenide substrate of either of the above-discussed origins, thedeposition of a uniform, single crystal, epitaxial barium fluorideinsulator layer becomes straightforward. The rate of deposition ofbarium fluoride is no longer as critical. The uniform, single crystalepitaxial barium fluoride can be formed by depositing barium fluoridevapor on uniform, epitaxial barium fluoride/gallium arsenide reactionproduct coated substrates at temperatures of 400° C. to room temperatureat deposition rates of about 50-300 Å per minute. The crystalorientation of the uniform, single crystal epitaxial barium fluoridelayer is the same as that of the single crystal gallium arsenidesubstrate. For example, uniform (100) oriented single crystal epitaxialbarium fluoride layers are deposited on (100) oriented single crystalgallium arsenide substrates and uniform (111) oriented single crystalepitaxial barium fluoride layers are deposited on (111) single crystalgallium arsenide substrates. This means that the intervening monolayerreaction product layer is uniform and of the same crystal orientation asthe single crystal gallium arsenide substrate. If the single crystalgallium arsenide substrate surface has a (100) crystal orientation, thesingle crystal epitaxial barium fluoride layer will have a twodimensional (100) oriented structure as shown by RHEED pattern. On theother hand, if the single crystal gallium arsenide substrate surface hasa (111) crystal orientation, the single crystal epitaxial bariumfluoride layer will have a two dimensional (111) oriented structure asshown by RHEED pattern.

After the uniform monolayer is formed, the vacuum is maintained at abackground pressure of preferably less than 10⁻⁸ millibars, morepreferably less than 10⁻⁹ millibars, and still more preferably less than10⁻¹⁰ millibars. The barium fluoride is deposited at a rate ofpreferably 1 to 5 Å per second, and more preferably 2 to 3 Å per second.

Single crystal epitaxial layers of barium fluoride grown at temperaturesabove 500° C. contain small amounts of gallium on the order of 1 to 50ppm. It is has been found that these traces of gallium do not adverselyaffect the insulative properties of the barium fluoride layer. Galliumcontaining barium fluoride (1052 Å thick) produced at 600° C. has acapacitance of 550.0 pF, an average breakdown voltage above 8×10⁶ V/cm,and a dielectric constant of ∥7.5 which is close to that of bulk bariumfluoride. Depositing barium fluoride on the uniform monolayer attemperatures of 400° C. or lower produces a single crystal epitaxialbarium fluoride layer that is free of gallium. However, the insulatingproperties of the gallium-containing and the gallium-free bariumfluoride layers are the same. Therefore the term barium fluoride layeras used in describing the improved devices (capacitors, MISFETs, CCDs,etc.) of this invention includes both gallium-containing and galliumfree barium fluoride.

The term single crystal gallium arsenide substrate, as used herein,preferably includes doped or undoped gallium arsenide single crystalwafers, doped or undoped gallium arsenide epitaxial layers on galliumarsenide single crystal wafers, doped or undoped epitaxial layers ofgallium arsenide alloys (for example, gallium aluminum arsenide, galliumindium arsenide, and so forth) on single crystal gallium arsenidewafers, heterostructures of super-lattice made of combinations ofgallium arsenide alloys on gallium arsenide single crystal wafers, dopedor undoped gallium arsenide single crystal epitaxial layers on suitablesubstrate materials, doped or undoped epitaxial layers of galliumarsenide alloys on suitable substrate materials, and heterostructures ofsuper-lattice made of combinations of gallium arsenide alloys onsuitable substrate materials. More preferably the single crystal galliumarsenide substrate includes doped or undoped gallium arsenide singlecrystal wafers, doped or undoped gallium arsenide epitaxial layers ongallium arsenide single crystal wafers, and doped or undoped galliumarsenide single crystal epitaxial layers on suitable substratematerials. The gallium arsenide alloys include those that areconventionally used in semiconductor devices. Gallium arsenide alloysthat are rich in gallium are preferred. The suitable substrate materialsinclude materials that provide physical support for a thin epitaxiallayer of gallium arsenide or gallium arsenide alloys without chemicallyor electrically interfering with the operation of the epitaxial layer.For example, a thin single crystal epitaxial layer of gallium arsenideon a hybrid semiconductor device or on a chemically inert, electricallyinsulating circuit board structure. Thus, the single crystal galliumarsenide substrate need not be a wafer but rather can be a thinepitaxial layer requiring support by a non-gallium arsenide material.The single crystal gallium arsenide substrate bulk stoichiometry may bebalanced, gallium rich, or arsenic rich.

However, because the single crystal gallium arsenide substrate is heatedat from 500° C. to 700° C. for substantial periods of time during theBaF₂deposition, some doping operations may have to be done after thebarium fluoride deposition to alter the doping profile of the dopedareas. The single crystal gallium arsenide substrate may have any of theconventional orientations including (100), (110), (111), and theirequivalents. Commercial standard electronic grade polished and etched(100) and (111) oriented crystal wafers are generally suitable for useas a starting material for the practice of this invention.

The commercial standard grade single crystal gallium arsenide substratewafers come with a polycrystalline oxide passivation layer that must beremoved. The presence of the polycrystalline passivation layer can bedetected by analytical techniques like x-ray photoelectron spectroscopy(XPS) and reflective high energy electron diffraction (RHEED). Thepassivation layer will show oxygen in the XPS spectrum and a RHEEDdiffraction pattern that shows scattered dots and concentric circles.Removal of the passivation layer leaves the bare gallium arsenidesurface whose smoothness is confirmed by the RHEED pattern that showsordered spots connected with streaks and the absence of oxygen in theXPS spectrum. Conventional methods for removing the passivation layermay be used. A preferred method is by annealing the gallium arsenide ina vacuum. The single crystal gallium arsenide wafers can be annealed inconventional annealing equipment, such as a VG Semicon V80H depositionchamber for one hour at approximately 600° C. in a vacuum of better than1×10⁻⁹ millibar. Prior to insulator film formation, the substratesurface morphology also can be improved using wet chemical etching andGaAs homoepitaxial deposition.

Referring now to the figures, FIG. 1 is a schematic drawing or a crosssection of a basic structure comprising a single crystal galliumarsenide semiconductor substrate 10; a homogenous layer 12, which iscomprised of the monolayer reaction product of the barium fluoride andgallium arsenide, covering a portion of the surface 11 of the singlecrystal gallium arsenide substrate 10; and a uniform, single crystalepitaxial barium fluoride insulator layer 14 which is deposited on themonolayer 12. The uniform monolayer 12 is less than about 5 Å thick. Forelectronic devices the uniform, single crystal epitaxial barium fluorideinsulator layer 14 normally will be from about 50 to 1000 Å thick, butlayers up to 10,000 Å are easy to produce if appropriate. In practice,the electrical properties of the extremely thin monolayer 12 may beignored and the structure may simply be considered to be a singlecrystal epilayer of barium fluoride 14 deposited on the single crystalGaAs substrate. This basic structure can be used to make integratedcircuit capacitors, metal insulator semiconductor field effecttransistors (MISFETS), charge couple devices (CCDs), and other types ofgallium arsenide electronic devices requiring a metal insulatorsemiconductor junction.

A structure of the type shown in FIG. 1 can be used as the dielectricportion of a gallium arsenide semiconductor integrated circuitcapacitor. Epitaxial barium fluoride is formed on the gallium arsenideto provide the dielectric insulator element of the capacitor and twometal electrodes are deposited on adjacent sites of the epitaxial bariumfluoride to form a metal insulator metal (MIM) integrated circuitcapacitor. Similarly, by depositing one metal on top of the singlecrystal epitaxial barium fluoride layer and another electrode on thegallium arsenide semiconductor a metal insulator semiconductor (MIS)capacitor can be produced. A similar procedure can be used to produce asemiconductor insulator semiconductor (SIS) capacitor.

The basic barium fluoride epitaxial insulator layer 14 and singlecrystal gallium arsenide semiconductor substrate 10 structure shown inFIG. 1 can also be used as the basis of an improved gallium arsenidemetal insulator semiconductor field effect transistor (MISFET). Theelement may be used to make depletion mode MISFETs as well asenhancement mode MISFET's. This will include n-channel depletion modeMISFET's, p-channel depletion mode MISFET's, n-channel enhancement modeMISFET's, and p-channel enhancement mode MISFET's.

FIG. 2A is a schematic drawing representing a depletion mode MISFETaccording to this invention. Shown are a single crystal gallium arsenidesemiconductor substrate 20 which has been doped to produce a sourceregion 22, a drain region 24, and a channel region 26. The channelregion 26 connects the source region 22 to the drain region 24. An ohmicsource electrode 28 is deposited onto the source region 22 and an ohmicdrain electrode 29 is deposited onto the drain region 24. An insulatorepitaxial barium fluoride layer 23 is deposited on the surface 27 of thesingle crystal gallium arsenide semiconductor substrate 20 over thechannel region 26 via an intervening monolayer 21 according techniquesdescribed herein. A gate electrode 25 is deposited onto the bariumfluoride epitaxial layer 23 so that the barium fluoride layer 23insulates the gate electrode 25 from the channel region 26. As will beunderstood, the above-mentioned ohmic source and drain electrodes, andthe gate electrode, are formed of a highly conductive material such asmetal or a highly doped semiconductor. The thin monolayer reactionproduct zone 21 is shown between the barium fluoride epitaxial layer 23and the channel region 26 of the single crystal gallium arsenidesemiconductor substrate 20. The monolayer 21, which is the reactionproduct of the gallium arsenide surface and barium fluoride, will notsignificantly affect the operation of the MISFET device. FIG. 2B is aschematic drawing representing an enhancement mode MISFET according tothis invention. The labeled parts are the same as in FIG. 2A except thatthe channel, region 26 is normally off until application of anappropriate voltage on the gate 25.

The relatively high temperature (500° C. or above) of the presentprocess, may require that certain doping steps be performed after thebarium fluoride epitaxial layer has been grown. However, the singlecrystal gallium substrate under the barium fluoride layer may be dopedby using conventional ion beam implantation techniques. The dopant ionswill pass through the barium fluoride layer and be implanted in thesingle crystal gallium arsenide substrate. The single crystal galliumarsenide substrate will then be annealed to diffuse the dopant ions inthe single crystal gallium arsenide substrate. For example, a MISFETdevice may be produced by combining the present process within beamimplantation as follows. First, a barium fluoride epitaxial crystalinsulator layer is grown on a single crystal gallium arsenide substrateaccording to the process of this invention. Holes are left in the bariumfluoride film for source and drain regions. The source and drain regionsare then doped according to conventional techniques. Metal electrodesare then deposited onto the source and drain regions. Next an ion beamis used to implant dopant ions through the barium fluoride film into thesingle crystal gallium arsenide substrate. The metal electrodes protectthe source and drain regions from the ion beam. The single crystalgallium arsenide substrate is annealed to diffuse the ion implanteddopant to complete the doping of the channel region.

The process and products of the present invention are designed to beused to produce large scale integrated circuits. For example, thisincludes large scale computer logic and control circuit arrayscontaining many depletion mode MISFETS, enhancement mode MISFETs, MIMcapacitors, and so forth. It also includes large scale memory arrayscontaining many charge couple devices and associated circuitry.

FIG. 3 is a schematic drawing representing a charge coupled device (CCD)according to this invention. Shown is a p-type single crystal galliumarsenide wafer 30 with or without an epitaxial layer of single crystalgallium arsenide. An insulator barium fluoride epitaxial layer 34 isdeposited onto the surface 38 of the gallium arsenide wafer 30 via anintervening monolayer 33 according techniques described herein. The thinmonolayer 33, which is the reaction product of the gallium arsenide andbarium fluoride, is shown located between the barium fluoride epitaxiallayer 34 and the gallium arsenide wafer 30. The reaction product layer33 (i.e., monolayer 33) will not significantly affect the operation ofthe charge coupled device. Metal gate electrodes 35, 36, and 37 aredeposited onto the barium fluoride epitaxial layer 34 so that the bariumfluoride epitaxial layer 34 insulates the metal gate electrodes 35, 36,and 37 from the p-type single crystal gallium arsenide wafer 30. Themetal gate electrodes 35, 36, and 37 serve as gates for the chargetransfer signals. When gate 36 has a higher (more positive) voltage thangates 35 and 37, the charges 31 are concentrated in region 32 just belowgate 36 which serves as a charge storage. When either gate 35 or 37 ispulsed to a higher (more positive) voltage than gate 36 the charge 31will be transferred to the pulsed gate. The device shown in FIG. 3 isjust an illustrative example of how to use the present invention incharge couple devices, different schemes and layouts can be used for thecharge couple devices.

FIGS. 4A and 4B are schematics of several configurations of capacitordevices according to this invention. Shown is a doped single crystalgallium arsenide wafer 40 with or without an epitaxial layer of singlecrystal gallium arsenide. An insulator barium fluoride epitaxial layer42 is deposited onto the surface 45 of the gallium arsenide wafer 40 viaintervening thin monolayer 41 according to the techniques describedherein. The thin monolayer 41 is the reaction product of the galliumarsenide and barium fluoride and it is located between the bariumfluoride epitaxial layer 42 and the gallium arsenide wafer 40. Metalelectrode 43 is deposited on the barium fluoride epitaxial layer 42 andmetal electrode 44 is deposited on the same or opposite side of thesingle crystal gallium arsenide wafer 40.

FIG. 6 is a schematic drawing representing a nonvolatile memoryaccording to this invention. This present invention is also applicableto nonvolatile memory devices, such as a floating-gate nonvolatilememory as shown in FIG. 6. This device is somewhat similar to MISFETsexemplified in FIGS. 2A and 2B above except for the added componentsincluding a highly conductive floating gate 70, a secondary insulator71, and a highly conductive gate electrode 65. FIG. 6 includes singlecrystal GaAs semiconductor substrate 60 and its surface 67, monolayer61, ohmic source region 62, insulator epitaxial barium fluoride 63,ohmic drain region 64, channel region 66, and highly conductivematerials 68 and 69 (e.g., metals). The floating gate 70 can hold chargefor an extended period of time even up to 100 years. When the floatinggate 70 is uncharged, and the gate electrode 65 has no voltage, thechannel of charge 66 will exist and conduct between the drain region 64and the source region 62. This represents two binary states for binarymemory applications. The floating gate 70 can be charged and dischargedby electrons from the channel 66 of enough energy to overcome the energybarrier presented by the insulator epitaxial barium fluoride 63, or bymaking the insulator 63 exceptionally thin (e.g., less than 10nanometers), by electrons from the channel 66 by tunneling through theenergy barrier presented by the insulator epitaxial barium fluoride 63.The direction of electron flow (to or from the floating gate 70) can becontrolled by the voltage on gate electrode 65. The electrons can obtainthe necessary energy by either applying sufficient voltage to the sourceregion 62 or the drain region 64, or by illumination with energeticphotons such as ultraviolet light. Such devices rely on unprecedentedcontrol of the insulator epitaxial barium fluoride 63 including itsthickness, purity, and uniformity which have been demonstrated in thisinvention.

In another embodiment of this invention, a useful intermediate productis produced by forming the uniform, thin monolayer reaction product ofbarium fluoride and gallium arsenide on a single crystal galliumarsenide substrate in the presence of arsenic gas according to themethod described above, and then removing the barium fluoride vaporsource. Single crystal epitaxial barium fluoride layers can then laterbe deposited on the barium fluoride/gallium arsenide reaction productlayer by the methods described above. Moreover, by depositing the bariumfluoride vapor at a temperature of from room temperature to 400° C., orpreferably from room temperature to 300° C. with the other conditions(deposition rate, vacuum) being the same, a uniform, single crystalepitaxial barium fluoride insulator layer is formed which is free ofgallium ions.

With reference to FIG. 5, a suitable test set up for measuring thecapacitance and the breakdown voltage of an insulator layer of thisinvention is shown. An array of a plurality of gold dots 51, which arefive in number for this illustration, is evaporated onto a (100)oriented single crystal epitaxial barium fluoride film 54 and acorresponding array of five (5) gold dots 52 is evaporated on to theadjoining edge of the (100) oriented single crystal gallium arsenidesubstrate 50 not exposed to the barium fluoride flux. Adjacent gold dots51 and 52 form pairs that are used in the measurements. Interconnectionwires, e.g., indium-soldered gold wires, are attached to the gold dots51 on the barium film 54 and to the gold dots 52 on the gallium arsenidesubstrate 50. Capacitance and breakdown voltage measurements then can bedone on all five pairs of adjacent gold dots (electrodes).

EXAMPLES Example 1

An insulator layer was grown on single crystal gallium arsenide film byMolecular Beam Epitaxy in a VG Semicon V80H deposition chamber accordingto the following protocol. The MBE system had Knudsen effusion cells,and a 30 kV RHEED system to monitor the film structure during filmdepositions. Heating of the GaAs substrate during film depositionoperations described below was performed by tantalum foil strips located1 cm above the back of the GaAs wafer. The temperature was measured by athermocouple located above these heater strips and out of physicalcontact with the heater, substrate holder, and wafer substrate.

A single crystal gallium arsenide substrate was used which was acommercial (100) oriented 2 inch (5.1 cm) diameter wafer with a carrierconcentration of approximately 3×10¹⁵ carriers/cm³ and arsenic togallium concentration ratio of approximately 50/50. The GaAs (100) waferwas chemically etched before being introduced to the growth chamberusing standard industry procedures.

With the GaAs substrate supported on a rotatable holder inside the MBEchamber trapped with LN₂, a GaAs (100) epilayer was then deposited onthe GaAs wafer surface by opening of the shutters of a gallium effusioncell and a separate arsenic effusion cell under conventional conditionsfor such GaAs epilayer film formation until a streaky reflective highenergy electron diffraction (RHEED) pattern was observed. Then, thegallium shutter was closed while leaving the arsenic shutter remainingopen.

Next, while maintaining the substrate at 650° C., a BaF₂ shutter wasopened to begin BaF₂deposition while the arsenic shutter remained open.For this deposition stage, the BaF₂ and the arsenic were supplied byseparate effusion cells located approximately 15 inches (38 cm) belowthe rotatable substrate holder and in which the respective cells hadbeen heated effective to provide an arsenic flux of 1.0×10⁻⁶ millibarand a BaF₂ flux of 1.0×10⁷ millibar in the MBE chamber.

15 seconds after the BaF₂ shutter was opened, then the arsenic shutterwas closed while the BaF₂ shutter was left open, and BaF₂ deposition waspermitted to proceed for 30 minutes while maintaining the substrate at650° C. before the BaF₂ shutter was closed. During the BaF₂ deposition,the RHEED pattern remained streaky throughout, with RHEED oscillationsclearly visible. After completing deposition of the BaF₂, the resultingGaAs wafer bearing the deposited films was cooled to room temperature in˜1 hour.

Based on RHEED patterns monitored during the above GaAs and BaF₂ filmgrowth sequence, the wet chemical etch and GaAs epilayer growth resultedin a two-dimensional surface (i.e., a flat surface: no out-of-planeimperfections at the surface level), and the epitaxial BaF₂ layerdeposited on the two-dimensional GaAs surface with arsenic overpressureduring the initial BaF₂ deposition was also two-dimensional. Bycontrast, insulator layers formed with a similar growth sequence exceptwithout including the arsenic gas treatment had spotty RHEED patternsindicative of surface level roughness for the insulator layer.Specifically, it was observed in additional experimental comparisonstudies that deviating from the above BaF₂ film deposition protocol byinterrupting the arsenic overpressure between the GaAs and BaF₂ filmdeposition stages for as little as 5 seconds caused the RHEED patternsof the GaAs layer and the subsequent BaF₂ layer to degrade to an extentcomparable to a rough epitaxial surface, which indicated thesignificance of the arsenic gas treatment.

The experimental results of the present invention are in sharp contrastto previous attempts by others discussed above in the Background sectionto grow (100) oriented and/or two-dimensional thin films of BaF₂on GaAs.

The present inventors also have found by heavy ion backscatteringspectroscopy that gallium and arsenic will diffuse into the BaF₂lattice, but the Ba layer created at the GaAs/BaF₂ interface acts as aneffective barrier against Ga and arsenic diffusion. The insulator layersof this invention have breakdown voltage fields in excess of 1×10⁷ V/cm.

In summary, the BaF. layers grown during the present investigation (at650° C.) were (100)-oriented throughout, and the RHEED patterns wereconsistently streaky with no rings or spots. The surface morphology ofthese (100)-oriented BaF,layers were two-dimensional (i.e.,flat-surfaced). This occurs despite the surface free energyconsiderations which seemingly favors (111)-oriented films, or at thevery least a (100)-orientation with exposed (111) facets. This suggeststhat surface free energy considerations are not applicable when anatomic template layer is employed for heteroepitaxy. Epitaxial BaF₂.(100) on a lattice mismatched substrate was made possible by chemicallymodifying the substrate surface before BaF₂ deposition. Thetwo-dimensional morphology of this layer was made possible bymaintaining the arsenic gas overpressure during the initial stages ofthe BaF₂. deposition.

While the invention has been shown and and described with reference tocertain preferred embodiments, it will be understood by those skilled inthe art that changes in form and detail may be made without departingfrom the spirit and scope of the appended claims.

What is claimed is:
 1. A method of forming an insulator on a singlecrystal gallium arsenide substrate, comprising the steps of: (a)providing a single crystal gallium arsenide substrate having a cleansubstrate surface in a chamber; (b) heating the single crystal galliumarsenide substrate in a vacuum formed within the chamber; (c)introducing arsenic gas within the chamber; (d) introducing a Group IIametal fluoride vapor into the chamber at a rate effective to form ahomogenous layer comprised of a monolayer of Group IIa atoms attacheddirectly onto said gallium arsenide substrate surface as the reactionproduct of a reaction between the Group IIa metal fluoride vapor and theclean substrate surface in the presence of the arsenic gas at saidsubstrate surface and such that the homogenous layer is substantiallyfree of Group IIa atoms unreacted with the gallium arsenide substratesurface when the monolayer is completed; (e) continuing introducingGroup IIa metal fluoride vapor into the chamber, after forming saidmonolayer in step (d), at a rate effective to deposit a single crystalepitaxial film of Group IIa fluoride onto the monolayer; and (f)discontinuing arsenic gas introduction during step (e).
 2. The method ofclaim 1, wherein the Group IIa fluoride vapor is introduced in step (e)at a rate producing a deposition rate of 1 to 5 Å per second for thesingle crystal epitaxial film of Group IIa metal fluoride.
 3. The methodof claim 1, wherein the Group IIa metal fluoride vapor is introduced instep (e) at a rate producing a deposition rate of 2 to 3 Å per secondfor the single crystal epitaxial film of Group IIa metal fluoride. 4.The method of claim 1, wherein said substrate surface is heated at from550 to 700° C. during steps (b), (c), (d) and (e).
 5. The method ofclaim 1, wherein the provided single crystal gallium arsenide substratesurface and the single crystal epitaxial Group IIa metal fluoride filmformed both are (100) oriented.
 6. The method of claim 1, wherein theprovided single crystal gallium arsenide substrate surface and thesingle crystal epitaxial Group IIa metal fluoride film formed both are(111) oriented.
 7. The method of claim 1, wherein the single crystalgallium arsenide substrate is selected from the group consisting ofgallium arsenide single crystal wafers, gallium arsenide epitaxiallayers on gallium arsenide single crystal wafers, and heterostructuresof super-lattice made of combinations of gallium arsenide alloys ongallium arsenide single crystal wafers.
 8. The method of claim 1,wherein said epitaxial film of Group IIa metal fluoride is deposited toa thickness ranging from 50 Å to 2500 Å, and said homogenous film isformed having a thickness of less than 5 Å.
 9. The method of claim 1, awherein said Group IIa metal atoms are barium atoms and said Group IIametal fluoride is barium fluoride.
 10. The method of claim 1, whereinsaid Group IIa metal atoms are calcium atoms and said Group IIa metalfluoride is calcium fluoride.
 11. The method of claim 1, wherein saidGroup IIa metal atoms are strontium atoms and said Group IIa metalfluoride is strontium fluoride.